EP1225166B1 - Verfahren zur Herstellung enantiomerenangereicherter Beta-Aminosäure - Google Patents

Verfahren zur Herstellung enantiomerenangereicherter Beta-Aminosäure Download PDF

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Publication number
EP1225166B1
EP1225166B1 EP01129076A EP01129076A EP1225166B1 EP 1225166 B1 EP1225166 B1 EP 1225166B1 EP 01129076 A EP01129076 A EP 01129076A EP 01129076 A EP01129076 A EP 01129076A EP 1225166 B1 EP1225166 B1 EP 1225166B1
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Prior art keywords
hydrogenation
alkyl
process according
cycloalkyl
carried out
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Expired - Lifetime
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German (de)
English (en)
French (fr)
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EP1225166A1 (de
Inventor
Hans-Peter Dr. Krimmer
Karlheinz Prof. Drauz
Jutta Dr. Lang
Armin Prof. Börner
Detlef Dr. Heller
Jens Dr. Holz
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention is directed to a method for Production of ⁇ -amino acids directed.
  • the method uses the method of enantioselective catalytic hydrogenation of prochiral N-acylated ⁇ -amino acrylic acids.
  • ⁇ -amino acids promise due to their structural Similarity to ⁇ -amino acids quasi analogs Behaviors. They are therefore an intensively researched one Area in the chemical and pharmaceutical industry, one hopes new bioactive ones through their use Manufacture active ingredients with improved characteristics can. Attention is paid to the enantioselective Production of the ⁇ -amino acids directed.
  • Noyori et al. also have corresponding ones Hydrogenation experiments carried out (tetrahedron: asymmetry 1991, 2, 543-554), but with less advantageous Respectively.
  • the process allows the corresponding hydrogenation products to be obtained in a comparatively short time and at lower pressures.
  • this process can implement both E and Z isomers of the compounds mentioned at lower pressures and in a shorter time, but with comparable good enantiomeric excesses, which makes the hydrogenation of E / Z mixtures possible.
  • This is of particular interest for the technical application of the process in question, since the isomer separation stage can now be omitted before the hydrogenation.
  • a method is also preferred in which the polar Solvent alcohols, e.g. Methanol, ethanol, Isopropanol, butanol, or ether, e.g. MTBE, THF, Esters, e.g. Ethyl acetate, acetoacetic ester, or halogenated solvents, e.g. Chloroform, Methylene chloride, or any mixture thereof starts.
  • the polar Solvent alcohols e.g. Methanol, ethanol, Isopropanol, butanol, or ether, e.g. MTBE, THF, Esters, e.g. Ethyl acetate, acetoacetic ester, or halogenated solvents, e.g. Chloroform, Methylene chloride, or any mixture thereof starts.
  • the polar Solvent alcohols e.g. Methanol, ethanol, Isopropanol, butanol, or ether, e.g. MT
  • the transition metals which are in the catalyst as the central atom for the reaction under consideration come, well known to the expert. Is preferred however, a process in which one as a catalyst Complex used, the transition metals Rh, Ru, Co, Ir in uncharged or ionic form.
  • Hydrogenation uses at least one polar Solvent molecule as a ligand in its ligand sphere exhibit. This will allow a faster exchange between Ligand (polar solvent molecule) and to be hydrogenated Reached substrate, which clearly shows the hydrogenation times helps lower (Fig. 1).
  • the enantioselective hydrogenation is preferably carried out by dissolving the substrate and catalyst to be hydrogenated, for example [Rh (MeDuPHOS) (MeOH) 2 ] BF 4 , in the polar solvent.
  • the catalyst is preferably formed from a precatalyst, for example [Rh (COD) 2 ] BF 4 , in the polar solvent in the presence of the chiral ligand by pre-hydrogenation before the substrate is added.
  • the mixture is then hydrogenated at 0.1 to 10 bar, preferably 0.5 to 5 bar, hydrogen pressure.
  • the temperature during the hydrogenation should be chosen so that the reaction proceeds sufficiently quickly at the desired enantiomeric excesses, but side reactions are avoided as far as possible. It is advantageous to work at temperatures from -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C.
  • the ratio of substrate to catalyst is determined by economic aspects determined.
  • the reaction is supposed to sufficiently quickly with as little as possible Be carried out catalyst concentration. Prefers however, one works with a substrate / catalyst ratio between 10,000: 1 and 10: 1, preferably 1000: 1 and 50: 1.
  • the compound (II) can be bound to a polymer increased molecular weight and thereby possibly be heterogenized.
  • the enantioselective hydrogenation with such substrates with increased molecular weight can therefore both in homogeneous and in heterogeneous phase take place.
  • connection can take place in a manner known to the person skilled in the art.
  • the connection in the formal (II) is advantageously carried out via the substituents R 1 or R 2 , but it can also be attached at another point in the molecule. This depends on the interaction that the polymer attachment exerts on the enantioselective reaction, which can be determined in routine experiments. It is advantageous that the compounds to be bound according to the invention are coupled to a suitable polymer via a linker in order to eliminate any disadvantageous interactions between the polymer and the complex which influence the catalytic reaction.
  • the manner of attachment to the polymer and the complex, and in relation to suitable polymers reference is made to the documents DE 100 296 01, DE 100 031 10, DE 100 029 73 and DE 100 029 76.
  • the complex or the ligand (I) or (II) can be used particularly advantageously in a membrane reactor, thereby creating the possibility of a quasi-continuous or continuous catalytic reaction (DE 199 10 691.6; Wandrey et al., Tetrahedron Asymmetry 1999 , 10, 923-928). This is particularly advantageous on a technical scale in terms of costs.
  • the ⁇ -amino acid precursors were prepared according to literature guidelines.
  • the general rules of Zhang et al. (G. Zhu, Z. Chen, X. Zhang J. Org . Chem. 1999, 64, 6907-6910) and Noyori et al. (WD Lubell, M. Kitamura, R. Noyori Tetrahedron: Asymmetry 1991 , 2 , 543-554) and Melillo et al. (DG Melillo, RD Larsen, DJ Mathre, WF Shukis, AWWood, JR Colleluori J. Org. Chem. 1987 52, 5143-5150).
  • the desired prochiral enamides were obtained by reaction with ammonium acetate and subsequent acylation.
  • the hydrogenation products can be converted into the ⁇ -amino acids by measures which are known to the person skilled in the art (analogously to the ⁇ -amino acids).
  • the (C 1 -C 8 ) alkyl radicals are methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl, tert- butyl, pentyl, hexyl, heptyl or octyl together with all of their binding isomers.
  • the radical (C 1 -C 8 ) alkoxy corresponds to the radical (C 1 -C 8 ) alkyl with the proviso that it is bonded to the molecule via an oxygen atom.
  • alkoxyalkyl radicals are meant in which the alkyl chain is interrupted by at least one oxygen function, it being impossible for two oxygen atoms to be bonded to one another.
  • the number of carbon atoms indicates the total number of carbon atoms contained in the rest.
  • a (C 2 -C 5 ) alkylene bridge is a carbon chain with two to five carbon atoms, this chain being bonded to the molecule under consideration via two different carbon atoms.
  • the radicals just described can be substituted one or more times with halogens and / or radicals containing N, O, P, S, Si atoms. These are in particular alkyl radicals of the type mentioned above which have one or more of these heteroatoms in their chain or which are bonded to the molecule via one of these heteroatoms.
  • Cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals etc. These can be containing one or more halogens and / or radicals containing N, O, P, S, or Si atoms be substituted and / or have N, O, P, S atoms in the ring, such as.
  • B. 1-, 2-, 3-, 4-piperidyl, 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl.
  • a (C 3 -C 8 ) cycloalkyl (C 1 -C 8 ) alkyl radical denotes a cycloalkyl radical as shown above, which is bonded to the molecule via an alkyl radical as stated above.
  • (C 1 -C 8 ) -acyloxy means an alkyl radical as defined above with a max. 8 carbon atoms, which is bound to the molecule via a COO function.
  • (C 1 -C 8 ) -acyl means an alkyl radical as defined above with a max. 8 carbon atoms, which is bound to the molecule via a CO function.
  • a (C 6 -C 18 ) aryl radical is understood to mean an aromatic radical with 6 to 18 C atoms.
  • these include compounds such as phenyl, naphthyl, anthryl, phenanthryl, biphenyl radicals or systems of the type described above fused to the molecule in question, such as indenyl systems, which may be substituted with (C 1 -C 8 ) alkyl, (C 1 -C 8 ) alkoxy, NR 1 R 2 , (C 1 -C 8 ) acyl, (C 1 -C 8 ) acyloxy may be substituted.
  • a (C 7 -C 19 ) aralkyl radical is a (C 6 -C 18 ) aryl radical bonded to the molecule via a (C 1 -C 8 ) alkyl radical.
  • a (C 3 -C 18 ) heteroaryl radical denotes a five-, six- or seven-membered aromatic ring system composed of 3 to 18 carbon atoms, which heteroatoms such as, for. B. has nitrogen, oxygen or sulfur in the ring.
  • heteroaromatics are, in particular, radicals such as 1-, 2-, 3-furyl, such as 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4- , 5-, 6-pyrimidinyl.
  • radicals such as 1-, 2-, 3-furyl, such as 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4- , 5-, 6-pyrimidinyl.
  • a (C 4 -C 19 ) heteroaralkyl is understood to mean a heteroaromatic system corresponding to the (C 7 -C 19 ) aralkyl radical.
  • Halogens are fluorine, chlorine, bromine and iodine Question.
  • PEG means polyethylene glycol
  • enantiomerically enriched is understood to mean the proportion of an enantiomer in a mixture with its optical antipode in a range from> 50% and ⁇ 100%.
  • the catalysts described here determine with their Configuration of the optical induction in the product. It it goes without saying that the catalysts are racemic also used to deliver racemic product. A subsequent racemate resolution then again provides the enantiomerically enriched products. However, this is in general knowledge of the specialist.
  • N-acyl groups are to be understood as protecting groups which common in amino acid chemistry for the protection of Nitrogen atoms are used. As such are special mention: formyl, acetyl, moc, eoc, phthalyl, Boc, Alloc, Z, Fmoc, etc.
  • the dashed line in formula (II) means one optional double bond.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP01129076A 2001-01-11 2001-12-07 Verfahren zur Herstellung enantiomerenangereicherter Beta-Aminosäure Expired - Lifetime EP1225166B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10100971 2001-01-11
DE10100971A DE10100971A1 (de) 2001-01-11 2001-01-11 Verfahren zur Herstellung enantiomerenangereicherter beta-Aminosäure

Related Child Applications (1)

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EP04006056 Division 2004-03-15

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EP1225166A1 EP1225166A1 (de) 2002-07-24
EP1225166B1 true EP1225166B1 (de) 2004-10-13

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US (1) US6492544B2 (enExample)
EP (1) EP1225166B1 (enExample)
JP (1) JP4301757B2 (enExample)
AT (1) ATE279388T1 (enExample)
DE (2) DE10100971A1 (enExample)

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US7007861B2 (en) 2000-06-08 2006-03-07 S.C. Johnson & Son, Inc. Methods and personal protection devices for repelling insects
BR0116160A (pt) * 2000-12-13 2003-10-14 Warner Lambert Co Ligandos bisfosfolano p-quirais e seus complexos com metais de transição
JP4226847B2 (ja) * 2001-07-24 2009-02-18 高砂香料工業株式会社 ホスフィン−ホスホラン化合物と遷移金属とを含有する遷移金属錯体の存在下、α，β−不飽和アミド誘導体から光学活性アミド類を製造する方法。
GB0120167D0 (en) * 2001-08-17 2001-10-10 Chirotech Technology Ltd Asymmetric hydrogenation
EP1451133B1 (en) * 2001-11-09 2017-10-25 The Penn State Research Foundation P-chiral phospholanes and phosphocyclic compounds and their use in asymmetric catalytic reactions
US7169953B2 (en) * 2001-11-09 2007-01-30 The Penn State Research Foundation P-chiral phospholanes and phosphocyclic compounds and their use in asymmetric catalytic reactions
JP2005529868A (ja) * 2002-04-04 2005-10-06 デグサ アクチエンゲゼルシャフト 二座配位子としてのビスホスフィン
US7084089B2 (en) * 2002-07-31 2006-08-01 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and a process for preparation of this bidentate diphosphine composition
US6806391B2 (en) 2002-07-31 2004-10-19 Shell Oil Company Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process
AR043515A1 (es) * 2003-03-19 2005-08-03 Merck & Co Inc Procedimiento para preparar derivados quirales beta aminoacidos mediante hidrogenacion asimetrica
TW200602293A (en) * 2004-04-05 2006-01-16 Merck & Co Inc Process for the preparation of enantiomerically enriched beta amino acid derivatives
US7013601B2 (en) * 2004-07-22 2006-03-21 Coastal Planters, Llc Plant container with hanger
US7618410B2 (en) * 2004-10-05 2009-11-17 Cardia Access, Inc. Devices and methods for access through a tissue wall
DE102005014055A1 (de) * 2005-03-23 2006-09-28 Degussa Ag Unsymmetrisch substituierte Phospholankatalysatoren
DE102005037649A1 (de) * 2005-08-05 2007-02-08 Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock Homogene katalytische Hydrierung
EP2070903A1 (en) 2007-12-12 2009-06-17 Laboratorios del Dr. Esteve S.A. Microwave-assisted ring opening reaction
EP2070904A1 (en) 2007-12-12 2009-06-17 Laboratorios Del. Dr. Esteve, S.A. Rhodium-phosphorus complexes and their use in ring opening reactions

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WO1999059721A1 (en) * 1998-05-18 1999-11-25 The Penn State Research Foundation Catalytic asymmetric hydrogenation, hydroformylation, and hydrovinylation via transition metal catalysts with phosphines and phosphites
EP1127061B1 (en) * 1998-11-05 2003-03-05 Chirotech Technology Limited Chiral ligands for asymmetric catalysis

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US6492544B2 (en) 2002-12-10
EP1225166A1 (de) 2002-07-24
US20020128509A1 (en) 2002-09-12
JP4301757B2 (ja) 2009-07-22
DE10100971A1 (de) 2002-07-18
ATE279388T1 (de) 2004-10-15
DE50104095D1 (de) 2004-11-18
JP2002265425A (ja) 2002-09-18

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